Resinous materials and method for the production thereof



Patented Aug. 14, 1945.

nnsmous MATERIALS sun METHOD For. I 'rna raonuc'rroN manor Kenneth M;Thompson, Aldan, Pa assignor to I The Atlantic Refining Company,Philadelphia, Pa., a corporation, of Pennsylvania No Drawing.Application May s, 1941, r SerlalNo. 391,715 I 12 Claims. (onto-s3)" Thepresent invention relates to the production of resinousmaterials fromhydrocarbon oils by reaction with aldehydes in the presence of acondensing agent'comprising an active boron compound.

An object of this invention isthe preparation of resins from petroleumoil distillates, and particularly cracked tar distillates containingcyclic hydrocarbons by reaction with. an aldehyde in the presence of acondensing agent from the group comprising BF: etherate, BF: alcoholate,dihydroxyfluoboric acid (BsBOzFa), dihydroxyfluoboric acid-boronfluoride addition compound (I-IsBOsFsBFa), or mixtures of two or more ofsuch agents.

A further object of this inventionis the preparation of modified resinsfrom petroleum oil fractions containing cyclic hydrocarbons by reactionwith -an aldehyde in the presence of a condensing agent 'of the typeaforementionedand the further reaction or condensation of the resultingproduct with an additional organic compound to modify the properties ofsuch product.

It has been proposed heretofore to prepare resinous materials byreacting aromatic hydrocarhang with aldehydes in the presence of strongcondensing agents such as HsSO4, FeCla, ZnCh, and AlCla. or by reactingcracked tar distillates or aromatic petroleum fractions with aldehydesin the presence of condensing agents such as 8:804, FeCla, ZnClz, andA101: which have been modified by the addition of a substantial quantityof a lower aliphatic acid such as acetic acid.

I have found that improved resins may be'produced in accordance with myinvention by reacting cyclic hydrocarbons or oils containing cyclichydrocarbons with aldehydes, in the presence of a condensing agentcomprising an active boron compound, and thatsuch resins are superior tothose produced by the prior artprocesses particularly with respect tocolor, softening point, resistance to alkalis, and resistance toweather- My process comprises essentially reacting an oil containingcyclic hydrocarbons with an aldehyde, in the presence of a condensingagent comprising an active-boron compound at a temperature sumcientlyelevated to effect reaction or chemical condensation of the ingredientsto form a resinous material. The resinous material, after removal of thecondensing agent, may be separated from unreacted oil by distillation\mder reduced pressure or by treatment with solvents. In onemodification of my process there may be added to the reaction-mixture orto the reaction product, during or after'thecompletion of the initialreaction, an additional chemical compound orcompounds to modify theproperties of the resinous product. g i

Resins may be prepared by my process from petroleum oils and coal taroils or fractions thereof containingsubstantial amountsof cycliclivdrocarbons and other, compounds having the property of condensingwith aldehydes. oils or fractions may be obtained bydistillation,solvent extraction, or other suitable means, of

naturallyoccurring petroleum oils or coal tar,-a'nd products ofcracking, oxidation, hydrogenatio dehydrogenation, destructivehydrogenation, or

chemical treatment thereof. Among the hydros carbons which maybeemployed are cracked or uncracked petroleum distillates, highzboilingoils from cracked tar, styrene, indene, and cumene, the polymersthereof, or oils containing such compounds, olefin polymers, terpenehydrocarbons, and alkylated aromatic hydrocarbon mixtures produced bythe hydrolysis of petroleum sludge sulfonic acids. Hydrocarbon oilscontaining cyclic hydrocarbons boiling approximately within the range offrom F. to'750 F., and

preferably within the range of 250 F. to 550 F.,'

are suitable for use in accordance with myinven tion. I have found thatimproved resins of light color may be prepared by subjecting thepetroleum friction to a preliminary treatment, with a refining agent inorder to remove the color-forming bodies and other highly activeconstituents which readily condense to form insoluble and infusiblebodies. The treated oil fraction partially or completely freed of suchbodies is then subiected to reaction with an aldehyde, in accordancewith my process. The'preliminary treatment maybe conducted with sulfuricacid, aluminum chloride, decolorizingadsorbents such as fullerfs earth.or bauxite, or other refining agents. This pretreatment should not becarried to such a degree as to remove any considerable quantity of theresin-forming constituents of the oil fraction.

Any aldehyde or compound containing analdehyde, group which has theproperty of condensing with cyclic hydrocarbons to form resinousmaterials may beemployed. The aldehydes may be used as such or inpolymerized form. Exemplary of these 'aidehydes are formaldehydaformalin paraformaldehyde, vacetaldehyde, propionaldehyde,butyraldehyde, valeric aldehyde, lyoxal glycolaldehyde, pyroracemicaldehyde,;aldo1, crotonaldehyde, acrolein, glyoxylic acid, furfural,

'benzaldehyde, cyclohexylaldehyde, andsaldehydes Suchproduced by thepartial oxidationof hydrocarbon oils and waxes.

In carrying out my condensation reactions to produce improved resinousmaterials, I use condensation agents or catalyst comprising an activeboron compound such as BF; etherate, alcoholate, HaBOzFaHaBOzFzBFa, andmixtures of BF: etherate and HaBOzFz. The quantity of condensing agentor catalyst utilized may vary from a few per cent up the reactants.

The BF: etherate may be produced by saturatto 25 percent byweight of inga lower aliphatic ether, suchas 'diethyl ether with BF:, and distillingthe productto obtain a fraction boiling between 255 F. and 260 F.comprising substantially BF: etherate. TheBFs alcoholate may be preparedin a similar manner,

phenols, the amyl phenols, and the petroleum phenols; the polyhydricalcohols and alcoholethers such as ethylene glycol, propylen glycol,ibutylene glycol, g cerol, diethylene glycol methyl, ethyl, propyl, andbutyl ethers; urea and the substituted ureas; thiourea andthesubstituted thioureas; and the aliphatic and aromatic monoandutilizing lower aliphatic alcohols such as methyl alcohol, ethylalcohol, or propyl alcohol.

The dihydroxyfluoboric acid (HaBOsFa) may-be prepared by two types ofreactions; First it may be preparedby the reaction of BF: upon solidboric acid (HaBOa). Asecond method comprises passing anhydroushydrofluoric acid (HzFa) into boricoxide (1320a) ,and heating to driveoff ZBFa.

The dihydroxyfluoboric acid-boron fluoride addition compound(HaBOsFmBFa) may bepre-fl pared by treating HsBOzFz' with a molecularlyequivalent amount of Bib. 1

In accordance with-my invention, the resin-' producing reaction may becarried out at temperatures between.150'F. and 400 F., and preferablybetween 175 Rand 250 F. Reaction timesmay vary from a few hours toseveral days, times of the order of 5to 15 .hoursi'being'preferred. Ingeneral, the reaction-when carried out for a diamines, including methyl,ethyl, propyl, butyl, and amyl amines, aniline, phenylene diamine;amides and diamides;- aliphatic and aromatic ketones; aliphatic andaromatic esters; fatty oils, and dryingoils such .astung oil, linseedoil, and the like. Polycarboxylic acids and anhydrides may also beemployed, including oxalic acid, succinic acid, malonic acid, 'glutaricacid, pyrotar homologues of this series.

relatively short time at high temperature prov duces dark coloredresins, whereas at lo er times and lower temperatures,'relatively lightcolored resins are obtained. The proportions of the re,- actantamay bevaried considerably, depending taric acid,,tartaric ,acid, pimelic acid,fumaric acid,maelic acid, adipic acid, phthallc acid, trif mesicacid,trimellitis acid,.amino polycarboxylic acids, mixtures of. two ormore of these acids, the anhydrides of such acidsor mixtures thereof. Inaddition to the polycarboxyiic acids and ,anhydrides, orin lieu thereof,I may employ monocarboxylicacids such as formic acid,'acetic acid,propionic acid, butyric acid, and the higher My'invention may befurtherillustrated by the examples given in the following table, which,however, are not to be construed; as limiting the scope thereof. Theprocedure employed in producing' the resins comprisedadmixing thereuponthe characteristics desired of the resinous products.Also,.depending upon the-composition and proportion of the reactants andupon the op-v I g the resinous product,';an d the benzene solutioncrating conditions, the resinous products obtained may range fromviscous. tacky material to hard,

solid materials of relatively high softening point. The rate of resinformation may be substantially increased by employing-an inert diluent'which functions as a mutual'solvent for the reactants,- therelbypermittingmore intimate contact between the reactants themselves as wellas the condensing agent. Mutual solvents such as chlorinatedhydrocarbons, i. e;, carbon tetrachloride, ethylene dichloride, and thelike, or lowboiling aromatic hydrocarbons such as benzene, have beenfound quite suitable. If desired, the-resins forming reaction may becarried outunder superactants andheating' the mixture,- with agitation,at the temperature and'for the time specified. ."I'he' reaction mixturewas'then cooled and diluted with 180 parts by weight of benzene todissolve was filtered free ofunneactedfsolid materials and.

condensation'agent, and thenthoroughly washed with water. 'I'hebenzene,and ,unreacted oil was distilled from the resinousfproduca the ultimatedistillation temperature being 550 F, at 3 mm.

hydrocarbons was distilled from a pressure still atmospheric pressure,for. example, pressuresup to several thousand-pounds per square inch, inorder tomaintain the reactants or mutuallsol vents substantially in theliquid phase.

In another aspect of my invention, I have found that I may modify theproperties of myresinous products by adding to the reaction mixture orto thereaction product, during or after completion of the initialreaction, an additional chemical compound or compounds capable ofenteringinto using 20 pounds of earth per barrel of, oil.

pressure. I

The 011 stocks used in-the examples were produced as vfollows: J

Stoclc- A.--An oil fraction containing cyclic cracked tar, and suchfraction was treated with 5 .pounds: of 66 H2804 ,per barrel .of

oil, and afterseparation of acid sludge, was

' filtered through 30-60 meshsi fullers earth,

Theresulting oil had" a distillation over point'of,

46891. at atmospheric pressure and an endpoint of 752F. at atmosphericpressure (over point of 218 'F. at 10 mm. pressure and endpoint 0f-'50 2F. at 10 mm.,pressure) 'an' A. P I. gravity of 185, a Sayb'olt Universalviscosity at 100 F. of seconds, an A. T. M. colorof 2, an'aniline p intof 106? F.. and a bromine number, of 11.

containing cyclic hydrocarbons-having a'd'istillation over point of 220F. and an end point of 435 F., and-an A. P. I. gravityof 52 .5 wastreated with 10 per cent by volume, of 9.8 percent H280; at 180 F. forhour. The treated oil was then sepathe ethyl phenols, the propylphenols, the butyl- Stock B.--Ast'raig ht run petroleum .naphtha' ratedfrom the acid sludge, and the acid sludge was diluted with per cent'byvolume of water, and the resulting dilute H2804 then separated from thearomatic suli'onic acid layer. The sulionic acids were then diluted withwater-and steamed at a temperature not exceeding 350 F., whereupon thesulionic acids were hydrolyzed to aiirylated aromatic hydrocarbons anddilute carbons with an aldehyde in the presence of a condensing agentirom the group consisting of H2804. The aromatic hydrocarbons were dis-'tilled from the hydrolysis mixture, and there was ethemte- B almhmate,and recovered an aromatic hydrocarbon traction hav- HIBOZFI-BFI- it atemperature p ct ve of the 1 ing a distillation over point of 275 F. andan end ns tion of cyclic hy s n the alpoint of 463 F., and A. P. I.gravity of 28.4", an dehyde to a usetul resinous material. 811111118Point 01 below F-, and an A. S. T. M. 3. A process which comprisesreacting a distilcolor of +19. v d late iraction'oi a cracked petroleumtar contain- I'he HaBOzFa condensation catalyst was prom cyclichydrocarbons with an aldehyde in the duced by reacting 2 moles of H330:with 1 mole presence of a condensing agent from the group of BFa, anddistilling the product to obtain a fracconsisting of BF; ethemte BF: 81coholate tion boiling between 311 F. and 320 F. comprism and Hmsm hemperature proing substantially HsBOzFa. The BF: etherate was ductive ofthe condensation of cyclic hydrocarproduced by saturating ethyl etherwith BF: and bong and m m h to, I i distilling the product to obtain afraction boiling rm e a 6 Y e a use mus between 255 F. and 260 F.comprising substante tially BF: etherate. The HaBOaFr-BF: etheratemethod rroducins resinous te iah was prepared by mixing equal parts ofHsBOaF: ch comprises reacting a p troleum ,oil fracand BF: etherate.tion containing cyclic hydrocarbons with an aide- Example12345075010111213 011 StockA partsby weight. 100 100 100 100 100 Stock d100 100 100 100 100 100 100 100 10.0, 25.2 25.3 25.3 25.2 31.0 13 20 2074 14 14 75 15 ii 13 34,7 s00 :IIIII III Temperature 115 220 220 220 220220 220 220 m Time -.hours 10 2 10 10 10 15 20 s 2 5 Resin Product Yield528 33.5 05.2 sac 47.0 50.0 51.0 5210 00.0 30.4 54.4 47.8 Boltenln point(B. 4111. 10 210 222 201 131 120 140 14:1 142 153 100 10s 0. D.coor2,050 2.015 1,000 as 15 100 105 as 110 02 1,510 Solubility in:

Benzene S S 8 8 B S B S S S S B 001. ssrssssssssss 48' petroleumnapbthe8 P8 P8 P8 5 S S S S S S S Petroleum ether P8 PS I I I B S 8 S S S 8 PSAcetone --PBPSSPBBSSSBBSBS Ethyialoohcl .-1 11111111111 S=soluble.Pfl=partly soluble. I=insolubla. 1

while in the above examples, I have shown the use of specific reactants,condensing agents, and quantities, as well as specific conditions forcarrying out my resin-producing process, it is to be understood that thereactants, quantities, and

conditions may be varied considerably, depending upon the propertiesdesired in the resinous products.

The resins of the present invention can be made in wide variety rangingfrom heavy viscous oils, which may be used in rubber compounding,adhesives, plastic compounds, and fly paper, to

' hard solids or high melting point, which find application in suri acecoating compositions, cast and moulded articles, such as enamels,varnishes, pipe coatings, inks, waterproofing, insulating compounds, andfloor tile.

What I claim is:

1. A process which comprises reacting a petroleum oil fractioncontaining cyclic hydrocarbone with an aldehyde in the presence of acondensing agent from the group consisting of BF: etherate, BF:alcoholate, HaBOzFa, and

at a temperature productive of the condensation of cyclic hydrocarbonsand the aldehyde to a useful resinous material.

6. I. resin produced by the reaction of a petroleum oil traction boilingwithin the range of 1mm F. to 750 1". and containing cyclic hydrocarbons.with formaldehyde in the presence of a condensing agent from the groupconsisting of BF: etherate, BF: alcoholate, W, and HJBOsFaBF: at atemperature or between 1''. and 400 I". d

7. A resin produced by the reaction of a distilants to a useful resinousmaterial.

late traction of a cracked petroleum tar boiling within the reuse orfrom 100' I". to 750 F; and containnig cyclic hydrocarbons withformaldehyde in the presence of a condensing agent from the groupconsisting of BF: etherate, B1 5 alcoholate, HsBOsFs, and HaBOzl 'aBFi,at a temperature or between 150 1''. and 400 F.

8. A process which comprises reacting a petroleum oil fractioncontaining cyclic hydrocarbons with a lower aliphatic aldehyde in thepresence of a condensing agent from the group consisting of B1":etherate, B1": alcoholate, HsBOsFs, and

HsBOsFmBFs. at a temperature productive oi the condensation of thecyclic hydrocarbons and the aldehyde to a useful resinous material. 1 9.A process which comprises reacting a petroleum oil fraction containingcyclic hydrocarbons BF: alccholate, HaBOzFa, and HsBOzFaBFs, and furtherreacting the resulting product with an aromatic hydroxy compound, saidreaction beingv conducted at a temperature productive of thecondensation of the reactants to a useful resinous material.

11. In a process of making a resin by the reaction of an aldehyde uponan aromatic hydro-- carbon, the step which comprises subjecting amixture of an aldehyde and an aromatic hydrocarbon to the condensinginfluence or a catalystselected from the group consisting of BF:etherate, BFa-alcoholate, HaBozFarand HaBOsFaBFs, at a temperatureproductive of the condensation of the reactants to a useful resin.

12. In a process of making a resin by the reaction 01' an aldehyde uponan aromatic hydrocarbon, the step which comprises subjecting a mixtureof an aldehydeand an aromatic hydrocarbon boiling within the range of100 I". to 750 F. to the condensing influence or a catalyst selectedfrom the group consisting oi BF: etherate, BF; alcoholate, HaBOsFs, andHaBOsFaBFa, at a temperature productive oi'-the condensation of thereactants to a usei'ul resin.

KENNETH M. THOMPSON.

